Method for the Treatment of Flexible Substrates

ABSTRACT

A process for treating substrates comprises contacting (A) at least one substrate selected from substrates composed of (A1) polyacrylic, polyester, silicone, polyamide or 
 
(A2) one or more polymers based on a monomer of the general formula I  
                 
         in each of which R 1  is selected from —Cl, C 1 -C 10 -alkyl, —CH═CH 2 , —C(Cl)═CH 2 , —C(CH 3 )═CH 2  and —COOC 1 -C 10 -alkyl, with at least one aqueous formulation comprising (B) at least one ethylene copolymer wax comprising from 60% to 95% by weight of ethylene and from 5% to 40% by weight of at least one ethylenically unsaturated carboxylic acid in interpolymerized form, further at least one colorant selected from (C) at least one pigment and (D) at least one dye.

The present invention relates to a process for treating flexible substrates, which comprises contacting

-   (A) at least one flexible substrate selected from substrates     composed of -   (A1) polyacrylic, polyester, silicone, polyamide or -   (A2) one or more polymers based on a monomer of the general formula     I     -   in each of which R¹ is selected from —Cl, C₁-C₁₀-alkyl, —CH═CH₂,         —C(Cl)═CH₂, —C(CH₃)═CH₂ and —COOC₁-C₁₀-alkyl,     -   with at least one aqueous formulation comprising -   (B) at least one ethylene copolymer wax comprising from 60% to 95%     by weight of ethylene and from 5% to 40% by weight of at least one     ethylenically unsaturated carboxylic acid in interpolymerized form,     further at least one colorant selected from -   (C) at least one pigment and -   (D) at least one dye.

Processes for coating, dyeing and printing flexible substrates such as for example foils or fibrous substrates such as for example wovens, formed-loop knits or nonwovens have demanding formulation requirements. One particular challenge relates to formulations relating to the printing of polypropylene for example. Polypropylene substrates printed with conventional formulations often exhibit inadequate fastnesses, for example as far as wash fastness and wet rub fastness are concerned. Similarly, other flexible substrates, composed of polyvinyl chloride or silicone for example, require treatment processes permitting for example printing or dyeing with good fastnesses.

Furthermore, there are for example limits to the adhesive bonding of polypropylene when temperatures above the melting or softening point of polypropylene are to be avoided in forming the adhesive bond. True, polypropylene can be modified by corona treatment such that an adhesive will subsequently hold. However, corona treatments are typically costly, usually not very efficient and have but limited stability for the modification in storage.

The present invention therefore has for its object to provide a process for treating flexible substrates without prior art disadvantages. The present invention further has for its object to provide treated flexible substrates. The present invention further has for its object to provide print pastes and dyeing liquors using which flexible substrates can be treated.

We have found that this object is achieved by the process defined at the beginning.

The process of the present invention starts from at least one substrate (A), substrates being preferably flexible substrates, i.e., substrates which can be manually deformed nondestructively, for example kinked, wound up, wound off, folded or bent, at room temperature at least once. Preferred examples of flexible substrates are textiles, hereinafter also referred to as textile substrates, foils and manually deformable hollow structures such as bottles for example.

Textiles or textile substrates for the purposes of the present invention are textile fibers, textile intermediate and end products and finished textile articles manufactured therefrom which, as well as textiles for the apparel industry, also include for example carpets and other home textiles and also textile structures for industrial purposes such as for example awnings. These also include unshaped structures such as for example staples, linear structures such as twine, filaments, yarns, lines, strings, cordage, threads and also three-dimensional structures such as for example felts, wovens, formed-loop knits, nonwovens, fleecestuffs and waddings.

Flexible substrates (A) are selected from substrates made from

-   (A1) polyacrylic, polyesters, silicones, polyamide, for example     polycondensates of α,ω-diamides with α,ω-dicarboxylic acids or     cyclic amides such as for example ε-caprolactam, or preferably -   (A2) one or more polymers based on a monomer of the general formula     I     in each of which R¹ is selected from -   chlorine,     -   C₁-C₁₀-alkyl, branched or unbranched, such as for example         methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,         sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,         neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl,         sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; more preferably         C₁-C₄-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,         isobutyl, sec-butyl and tert-butyl and most preferably methyl,     -   —CH═CH₂, —C(Cl)═CH₂, —C(CH₃)═CH₂     -   and —COOC₁-C₁₀-alkyl, wherein C₁-C₁₀-alkyl can be branched or         unbranched and as defined above.

Substrates composed of one of the foregoing polymers also include substrates comprising a certain fraction, for example not less than 30% by weight and preferably not less than 50% by weight, of at least one of the aforementioned polymers. Illustrative examples are blend fabrics composed of cotton-polyester or cotton-polyamide.

Polymers based on at least one monomer of the general formula I shall for the purposes of the present invention be taken to include not just homopolymers but also copolymers which may comprise a significant fraction, for example not less than 50 mol %, of at least one monomer of the general formula I in interpolymerized form. Useful copolymers also include for example ethylene-propylene copolymers which may contain not less than 50 mol % of propylene in interpolymerized form.

Very particular preference is given to substrates composed of polyvinyl chloride (PVC) and polypropylene (PP), which can each have been produced by any desired processes. Polypropylene for example can be produced by Ziegler-Natta catalysis or by metallocene catalysis.

According to the invention, at least one flexible substrate is contacted with at least one aqueous formulation comprising at least one ethylene copolymer wax comprising from

60% to 95% by weight and preferably from 65% to 85% by weight of ethylene and from 5% to 40% by weight and preferably from 15% to 35% by weight of at least one ethylenically unsaturated carboxylic acid in interpolymerized form, the weight %ages being based on the entire ethylene copolymer wax.

Preferably, at least one ethylenically unsaturated carboxylic acid is a carboxylic acid of the general formula II

where

-   R² is selected from hydrogen,     -   C₁-C₁₀-alkyl, such as methyl, ethyl, n-propyl, isopropyl,         n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,         sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,         isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; more         preferably C₁-C₄-alkyl such as methyl, ethyl, n-propyl,         isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;     -   COOH, COOCH₃, COOC₂H₅. -   R³ is selected from hydrogen,     -   C₁-C₁₀-alkyl, such as methyl, ethyl, n-propyl, isopropyl,         n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,         sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,         isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; more         preferably C₁-C₄-alkyl such as methyl, ethyl, n-propyl,         isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Most preferably, R² is hydrogen and R³ is hydrogen or methyl.

Ethylene copolymer waxes included in aqueous formulations used according to the present invention may comprise up to 40% by weight and preferably up to 35% by weight (each %age being based on the sum total of ethylene and interpolymerized ethylenically unsaturated carboxylic acid or acids) of one or more further monomers in interpolymerized form, for example

-   -   vinyl acetate,     -   one or more ethylenically unsaturated carboxylic esters,         preferably of the formula III

-   R⁴ is selected from hydrogen,     -   C₁-C₁₀-alkyl, such as methyl, ethyl, n-propyl, isopropyl,         n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,         sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,         isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; more         preferably C₁-C₄-alkyl such as methyl, ethyl, n-propyl,         isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;

-   R⁵ is selected from hydrogen,     -   C₁-C₁₀-alkyl, such as methyl, ethyl, n-propyl, isopropyl,         n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,         sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,         isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; more         preferably C₁-C₄-alkyl such as methyl, ethyl, n-propyl,         isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;     -   COOH, COOCH₃, COOC₂H₅,

-   R⁶ is selected from C₁-C₁₀-alkyl, such as methyl, ethyl, n-propyl,     isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,     isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl,     n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl;     more preferably C₁-C₄-alkyl such as methyl, ethyl, n-propyl,     isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Most preferably, R⁵ is hydrogen and R⁴ is hydrogen or methyl.

Most preferably, R⁵ is hydrogen and R⁴ is hydrogen or methyl and R⁶ is selected from methyl, ethyl, n-butyl and 2-ethylhexyl.

Foregoingly described ethylene copolymer waxes of ethylene and ethylenically unsaturated carboxylic acids can be prepared with advantage by free-radically initiated copolymerization under high-pressure conditions, for example in stirred high-pressure autoclaves or in high-pressure tubular reactors. The preparation in stirred high-pressure autoclaves is preferred. Stirred high-pressure autoclaves are known per se, a description is to be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, headwords: Waxes, Volume A 28, pages 146 et seq., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. Their length/diameter ratio varies predominantly in intervals from 5:1 to 30:1 and preferably 10:1 to 20:1. High-pressure tubular reactors, which can likewise be used, are likewise to be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, headwords: Waxes, Volume A 28, pages 146 et seq., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.

Suitable pressure conditions for the polymerization are 500 to 4000 bar, preferably 1500 to 2500 bar. The reaction temperatures range from 170 to 300° C. and preferably from 200 to 280° C.

The polymerization can be carried out in the presence of a regulator. Useful regulators include for example hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula IV

or mixtures thereof.

In the formula, R⁷ and R⁸ are the same or different and each selected from

-   -   hydrogen;     -   C₁-C₆-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,         isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,         sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,         isohexyl, sec-hexyl, more preferably C₁-C₄-alkyl such as methyl,         ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and         tert-butyl;     -   C₃-C₁₂-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,         cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,         cycloundecyl and cyclododecyl; preference is given to         cyclopentyl, cyclohexyl and cycloheptyl.

In one particular embodiment R⁷ and R⁸ are covalently bonded together to form a 4- to 13-membered ring. For example, R⁷ and R⁸ can conjointly be: —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆, —(CH₂)₇—, —CH(CH₃)—CH₂—CH₂—CH(CH₃)— or —CH(CH₃)—CH₂—CH₂—CH₂—CH(CH₃)—.

Very useful regulators include alkylaromatic compounds, for example toluene, ethylbenzene or one or more isomers of xylene. It is preferable not to use aldehydes and ketones of the general formula IV as regulator. It is particularly preferred not to add any further regulators with the exception of so-called phlegmatizers, which can be added to

organic peroxides to improve handling and can likewise have the function of a molecular weight regulator.

Useful initiators for the free-radical polymerization include the customary free-radical initiators such as for example organic peroxides, oxygen or azo compounds. Mixtures of two or more free-radical initiators are also suitable.

Suitable peroxides selected from the commercially available substances are

-   -   didecanoyl peroxide,         2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-amyl         peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl         peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate,         tert-butyl peroxydiethylisobutyrate,         1,4-di(tert-butylperoxycarbonyl)cyclohexane in the form of a         mixture of isomers, tert-butyl perisononanoate,         1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane,         1,1-di(tert-butylperoxy)cyclohexane, methyl isobutyl ketone         peroxide, tert-butyl peroxyisopropyl carbonate,         2,2-di-tert-butylperoxybutane or tert-butyl peroxyacetate;     -   tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumyl         peroxide, the isomeric di(tert-butylperoxyisopropyl)benzenes,         2,5-dimethyl-2,5-di-tert-butylperoxy-hexane, tert-butyl cumyl         peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne,         di-tert-butyl peroxide, 1,3-diisopropylbenzene         monohydroperoxide, cumene hydroperoxide or tert-butyl         hydroperoxide; or     -   dimeric or trimeric ketone peroxides of the general formula V a         to V c.

In these formulae R⁹ to R¹⁴ are the same or different and are each selected from

-   -   C₁-C₈-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,         sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl,         isopentyl, n-hexyl, n-heptyl, n-octyl; preferably linear         C₁-C₆-alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl,         n-hexyl, more preferably linear C₁-C₄-alkyl such as methyl,         ethyl, n-propyl or n-butyl, very particular preference being         given to ethyl;     -   C₆-C₁₄-aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,         2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,         3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably         phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.

Peroxides of the general formulae V a to V c and also processes for preparing them are known from EP-A 0 813 550.

Particularly suitable peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof. Illustrative of an azo compound is azobisisobutyronitrile (“AIBN”). Free-radical initiators are added in amounts customary for addition polymerizations.

Numerous commercially available organic peroxides are admixed with so-called phlegmatizers prior to sale in order to improve their handling. Examples of suitable phlegmatizers include white oil or hydrocarbons such as isododecane in particular. Under the conditions of free-radical high-pressure addition polymerization, such phlegmatizers can act to regulate molecular weight. For the purposes of the present invention, any reference to the use of molecular weight regulators should be taken to mean the additional use of further molecular weight regulators above and beyond the use of such phlegmatizers.

The ratio of the ethylene and ethylenically unsaturated carboxylic acid or acids monomers in the feed does not normally correspond exactly to the ratio of the units in the ethylene copolymer waxes included in the formulations used according to the present invention, since, generally speaking, ethylenically unsaturated carboxylic acids are more readily incorporated into ethylene copolymer waxes than is ethylene.

The monomers are typically metered together or separately.

The monomers can be brought to the polymerization pressure in a compressor. In another embodiment of the process according to the present invention the monomers are first brought to an elevated pressure of for example 150 to 400 bar, preferably 200 to 300 bar and especially 250 bar by means of a pump and are then brought to the actual polymerization pressure using a compressor.

The polymerization can be selectively carried out in the absence and in the presence of solvents; in this context, for the purposes of the present invention, mineral oils, white oil and other solvents which are present in the reactor during the polymerization and have been used to phlegmatize the free-radical initiator or initiators are not considered to be solvents.

In one embodiment the polymerization is carried out in the absence of solvents.

It is also possible, of course, to prepare ethylene copolymer wax by first copolymerizing ethylene with at least one ethylenically unsaturated carboxylic ester of the general formula III and then to saponify the ester groups in a polymer-analogous reaction, for example with aqueous potassium hydroxide solution or aqueous sodium hydroxide solution.

Aqueous formulations used according to the present invention preferably comprise from 0.05% to 40% by weight and preferably from 10% to 35% by weight of one or more ethylene copolymer waxes, preferably in fully or partially neutralized form.

To effect partial or full neutralization, aqueous formulations used according to the present invention typically comprise one or more substances having a basic action, for example hydroxides and/or carbonates and/or bicarbonates of alkali metals, ammonia, organic amines such as for example triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N,N-dimethylethanolamine. Aqueous formulations used according to the present invention preferably comprise a sufficient amount of basic substance or substances that at least half and preferably at least three quarters of the carboxyl groups of the ethylene copolymer wax or waxes are neutralized. Basic substances can be added to formulations used according to the present invention during the dispersing of ethylene copolymer wax for example.

In one embodiment of the present invention aqueous formulations used according to the present invention comprise a sufficient amount of basic substance or substances that the carboxyl groups of the ethylene copolymer wax or waxes are quantitatively neutralized.

Aqueous formulations used according to the present invention typically have a basic pH, preferably a pH in the range from 7.5 to 14, more preferably a pH of 8 or higher and most preferably a pH of 8.5 or higher.

Aqueous formulations used according to the present invention preferably do not include protective colloids. Aqueous formulations used according to the present invention are stable even without such surface-active auxiliaries; i.e., when sheared at 100 cm⁻¹ the light transmissivity of a dispersion having a solids content of 0.1% will not change by more than 2%, measured against pure water as reference.

Aqueous formulation used according to the present invention as well as ethylene copolymer wax (B) comprises

at least one colorant selected from

-   (C) at least one pigment and -   (D) at least one dye.

Pigments (C) for the purposes of the present invention are virtually insoluble, finely dispersed, organic or inorganic colorants as per the definition in German Standard Specification DIN 55944. It is preferable to select at least organic pigment and/or metal pigment.

Illustrative examples of organic pigments are monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1, 63, 112, 146, 170, 184, 210, 245 and 251; C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183; disazo pigments: C.I. Pigment Orange 16, 34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188; anthanthrone pigments: C.I. Pigment Red 168 (C.I. Vat Orange 3); anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31; anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31; anthrapyrimidine pigments: C.I. Pigment Yellow 108 (C.I. Vat Yellow 20); quinacridone pigments: C.I. Pigment Red 122, 202 and 206; C.I. Pigment Violet 19; quinophthalone pigments: C.I. Pigment Yellow 138; dioxazine pigments: C.I. Pigment Violet 23 and 37; flavanthrone pigments: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1); indanthrone pigments: C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue 6); isoindoline pigments: C.I. Pigment Orange 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185; isoindolinone pigments: C.I. Pigment Orange 61; C.I. Pigment Red 257 and 260; C.I. Pigment Yellow 109, 110, 173 and 185; isoviolanthrone pigments: C.I. Pigment Violet 31 (C.I. Vat Violet 1); metal complex pigments: C.I. Pigment Yellow 117, 150 and 153; C.I. Pigment Green 8; perinone pigments: C.I. Pigment Orange 43 (C.I. Vat Orange 7); C.I. Pigment Red 194 (C.I. Vat Red 15); perylene pigments: C.I. Pigment Black 31 and 32; C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23), 190 (C.I. Vat Red 29) and 224; C.I. Pigment Violet 29; phthalocyanine pigments: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16; C.I. Pigment Green 7 and 36; pyranthrone pigments: C.I. Pigment Orange 51; C.I. Pigment Red 216 (C.I. Vat Orange 4); thioindigo pigments: C.I. Pigment Red 88 and 181 (C.I. Vat Red 1); C.I. Pigment Violet 38 (C.I. Vat Violet 3); triarylcarbonium pigments: C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81:1 and 169; C.I. Pigment Violet 1, 2, 3 and 27; C.I. Pigment Black 1 (aniline black); C.I. Pigment Yellow 101 (aldazine yellow); C.I. Pigment Brown 22.

Examples of particularly preferred pigments (C) are: C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3 and 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.

Further suitable pigments (C) are metallic pigments such as for example gold bronze, silver bronze, Iriodin pigments, mica.

The median diameter of pigment (C) used in the process of the present invention is typically in the range from 20 nm to 1.5 μm and preferably in the range from 300 to 500 nm.

In one embodiment of the present invention pigment (C) used in the process of the present invention is present in a spherical or substantially spherical particulate form, i.e., the ratio of longest diameter to smallest diameter is in the range from 1.0 to 2.0 and preferably up to 1.5.

In another embodiment of the present invention pigment (C) used in the process of the present invention is present in the form of needles or pins.

Suitable dyes (D) are all textile dyes, for example vat dyes such as for example indigo and its derivatives, direct dyes, disperse dyes, acid dyes, metallized dyes, naphthol dyes, sulfur dyes, reactive dyes and pigment dyes.

Aqueous formulations used according to the present invention may be produced for example as described hereinbelow. One option is first to disperse one or more ethylene copolymer waxes in water. One or more of the ethylene copolymer waxes described above can be used for this. This is placed in a vessel, for example a flask, an autoclave or a tank. In one version the ethylene copolymer wax or waxes heats to above its melting point. It is advantageous to heat to a temperature not less than 10° C. and more advantageously to a temperature not less than 30° C. above the melting point of the ethylene copolymer wax or waxes. When a plurality of different ethylene copolymer waxes are used, they are heated to a temperature above the melting point of the ethylene copolymer wax melting at the highest temperature. In the case of a plurality of different ethylene copolymer waxes being used, it is advantageous to heat to a temperature not less than 10° C. above the melting point of the ethylene copolymer wax melting at the highest temperature. In the case of a plurality of different ethylene copolymer waxes being used, it is particularly advantageous to heat to a temperature not less than 30° C. above the melting point of the ethylene copolymer wax melting at the highest temperature.

Water and one or more basic substances and if appropriate further constituents such as for example ethylene glycol are then added in any order for the addition of water and the addition of basic substance or substances and also of further constituents. When the temperature is above 100° C., it is advantageous to operate under elevated pressure and to select the vessel accordingly. The resulting emulsion is homogenized, for example by mechanical or pneumatic stirring or by shaking. The aqueous formulation thus produced can subsequently be cooled down.

Thereafter, at least one colorant selected from (C) at least one pigment and (D) at least one dye can be added. Thereafter, water, ethylene copolymer wax (B) and colorant are mixed.

To add at least one pigment (C) as colorant, it is preferable to add pigment (C) in the form of a so-called pigment preparation, i.e., a form dispersed with water and if appropriate at least one surface-active material.

The present invention's process for treating flexible substrates is carried out by contacting at least one flexible substrate (A) with at least one aqueous formulation used according to the present invention.

In one embodiment of the present invention (A) is contacted with aqueous formulation at temperatures in the range from 20 to 100° C. and preferably at room temperature.

In one embodiment of the present invention the contacting is effected at pressures in the range from 0.5 bar to 10 bar and especially at atmospheric pressure.

In one embodiment of the present invention (A) is contacted with aqueous formulation at temperatures in the range from 70 to 180° C. and preferably from 90° C. to 120° C. and pressures above atmospheric pressure, for example up to 10 bar, are employed for this.

Contacting according to the present invention can be done for example for a period in the range from 0.1 second to 60 minutes and preferably from 0.5 second to 30 minutes.

The contacting of substrate (A) with aqueous formulation used according to the present invention can be done for example by spraying on, padding, coating, impregnating and printing, for example by the inkjet process.

Substrate (A) can be contacted one or more times in succession with aqueous formulation used according to the present invention.

The process of the present invention is preferably carried out by flexible substrate being contacted with at least one aqueous formulation used according to the present invention and subsequently dried.

It is particularly preferable for the actual drying to be preceded by predrying substrate treated according to the present invention, for example to a residual moisture content in the range from 0.5% to 2% by weight.

Predrying/drying can be carried out on commonly used apparatuses. To treat textile substrates, for example, predrying/drying can be carried out on all setting and drying assemblies customary in the textile industry. Suitable drying or predrying temperatures range for example from 50 to 300° C., and preferably from 70 to 180° C.

This may be followed by a thermal treatment at temperatures in the range from 50 to 300° C., preferably in the range from 100 to 160° C. and more preferably in the range from 110 to 130° C. for a period ranging for example from 10 seconds to 60 minutes, preferably from 0.5 minute to 7 minutes. Polyamide, polyester, polyvinyl chloride, modified polyesters, polyester blend fabrics, polyamide blend fabrics, polyacrylonitrile, polycarbonate are advantageously treated thermally at temperatures in the range from 130 to 250° C. Polypropylene fabrics preferably between 80 and 130° C. and more preferably between 110 and 130° C. Here temperature generally refers to the temperature of the medium surrounding the flexible substrate to be treated.

In one embodiment of the present invention aqueous formulation used according to the present invention comprises at least one further material (E) which can be selected from thickeners, crosslinkers, fastness improvers, plasticizers, defoamers, wetting agents and leveling agents.

Useful crosslinkers include for example urea-formaldehyde and melamine-formaldehyde addition products, if appropriate in combination with inorganic salts such as for example MgCl₂. 6H₂O or NH₄Cl. Useful crosslinkers further include for example free or blocked isocyanates or polyisocyanates such as for example compounds of the general formula VI

where

-   Y¹ is selected from N—R¹⁵, oxygen and N—H, -   Z¹ is selected from hydrogen and CO—O—R¹⁵, -   R¹⁵ is at each occurrence the same or different and selected from     C₁-C₁₀-alkyl, particular preference being given to methyl and     n-butyl.

Useful crosslinkers further include multiply functional epoxides such as for example polyglycidyl ethers of polyols, for example pentaerythritol polyglycidyl ether, and also multiply functional aziridines such as for example trimethylolpropane tris(beta-aziridinyl propionate).

Film inhibitors can be added for example to inhibit the formation of films on rolls of for example pad-mangles during contacting. Useful film inhibitors include for example mixtures of multiply alkoxylated alcohols, especially mixtures of multiply ethoxylated fatty alcohols.

As thickeners (thickening agent) there may be used natural or synthetic thickeners. Examples of natural thickeners are alginate, guar, starch, carob bean flour ether, cassia, tamarind cellulose ether, dextrins such as for example natural gums, galactomannan, xanthan, polysaccharide and mixtures thereof. Preference is given to the use of synthetic thickeners, for example to the use of room temperature liquid solutions of synthetic (co)polymers in for example white oil or as aqueous solutions or as water-in-oil emulsions, preferably comprising about 40% by weight of (co)polymer.

Preferred examples of thickeners are copolymers comprising from 85% to 95% by weight of acrylic acid, from 4% to 14% by weight of acrylamide and about 0.01-1% by weight of the (meth)acrylamide derivative of the formula VII

and having molecular weights M_(w) in the range from 100,000 to 200,000 g/mol, in each of which R¹⁶ is methyl or preferably hydrogen.

Formulations according to the present invention may comprise from 30% to 70% by weight of white oil. Aqueous thickeners comprise typically in total up to 25% by weight of (co)polymer and in some cases up to 50% by weight (so-called thickener dispersions), based on the entire thickener. When it is desired to use aqueous formulations of a thickener, aqueous ammonia is generally added. Even the use of granular, solid formulations of a thickener are conceivable in order to be able to produce pigment prints emissionlessly for example.

Useful fastness improvers include for example room temperature liquid silicone oils and polysiloxanes. In a preferred version of the present invention the use of fastness improvers can be dispensed with.

Examples of suitable plasticizers are ester compounds selected from the groups of the aliphatic or aromatic di- or polycarboxylic acids fully esterified with alkanols and of at least singly alkanol-esterified phosphoric acid.

In one embodiment of the present invention alkanols are C₁-C₁₀-alkanols.

Preferred examples of fully alkanol-esterified aromatic di- or polycarboxylic acids are fully alkanol-esterified phthalic acid, isophthalic acid and mellitic acid; illustrative examples are: di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.

Preferred examples of fully alkanol-esterified aliphatic di- or polycarboxylic acids are for example dimethyl adipate, diethyl adipate, di-n-butyl adipate, diisobutyl adipate, dimethyl glutarate, diethyl glutarate, di-n-butyl glutarate, diisobutyl glutarate, dimethyl succinate, diethyl succinate, di-n-butyl succinate, diisobutyl succinate and also mixtures thereof.

Preferred examples of at least singly alkanol-esterified phosphoric acid are C₁-C₁₀-alkyl di-C₆-C₁₄-aryl phosphates such as isodecyl diphenyl phosphate.

Further suitable examples of plasticizers are aliphatic or aromatic di- or polyols at least singly esterified with C₁-C₁₀-alkylcarboxylic acid at least singly.

2,2,4-Trimethylpentane-1,3-diol monoisobutyrate is preferred examples of aliphatic or aromatic di- or polyols esterified with C₁-C₁₀-alkylcarboxylic acid at least singly.

Further suitable plasticizers are polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably having an M_(w) of 200 g/mol, and polypropylene glycol alkylphenyl ether, preferably having an M_(w) of 450 g/mol.

Further suitable plasticizers are polypropylene glycols etherified with two different alcohols and having a molecular weight M_(w) in the range from 400 to 800 g/mol, wherein preferably one of the alcohols may be an alkanol, especially a C₁-C₁₀-alkanol, and the other alcohol may preferably be an aromatic alcohol, for example o-cresol, m-cresol, p-cresol and especially phenol.

Useful defoamers include for example silicone-containing defoamers such as for example those of the formula HO—(CH₂)₃—Si[OSi(CH₃)₃]₂. Silicone-free defoamers are also suitable, such as for example multiply alkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-tuply ethoxylated preferably unbranched C₁₀-C₂₀-alkanols, unbranched C₁₀-C₂₀-alkanols and 2-ethylhexan-1-ol.

Useful wetting agents include for example nonionic, anionic or cationic surfactants, especially ethoxylation and/or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, also ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkyl phosphonates, alkylphenyl phosphonates, alkyl phosphates or alkylphenyl phosphates.

Useful leveling agents include for example block copolymers of ethylene oxide and propylene oxide having molecular weights M_(n) in the range from 500 to 5000 g/mol, and preferably in the range from 800 to 2000 g/mol. Particular preference is given to block copolymers of propylene oxide/ethylene oxide for example of the formula EO₈PO₇EO₈, where EO represents ethylene oxide and PO represents propylene oxide.

The present invention further provides substrates treated by the process of the present invention. Substrates according to the present invention comprise at least one ethylene copolymer wax in crosslinked or uncrosslinked form. Substrates according to the present invention have good performance characteristics, for example good fastnesses, especially wash fastnesses and rub fastnesses such as for example dry and wet rub fastness.

A specific embodiment of the present invention is a process for producing printed flexible substrates and especially printed textile by the process of the present invention, hereinafter also referred to as inventive textile printing process.

The inventive textile printing process can be carried out for example by processing at least one inventive aqueous formulation to form a print paste, hereinafter also referred to as inventive print paste, and thereafter printing textile substrates by methods known per se.

Inventive print pastes are advantageously produced by mixing at least one aqueous formulation used according to the present invention with common printing-process auxiliaries and at least one pigment (C). The depth of shade is advantageously controlled by adjusting the ratio of pigment (C) to aqueous formulation used according to the present invention.

Pigment is preferably added to the inventive print paste in the form of pigment preparations. Pigment preparations customarily comprise from 20% to 60% by weight of pigment, water and one or more surface-active compounds, for example one or more emulsifiers, examples being multiply alkoxylated C₁₀-C₃₀-alkanols.

The ratio of pigment to aqueous formulation used according to the present invention can be varied within wide limits. For instance, pigment and aqueous formulation used according to the present invention can be used in a weight ratio of 20:1 to 1:100. In a preferred embodiment of the present invention the ratio of pigment to aqueous formulation used according to the present invention is adjusted such that the weight ratio of pigment to solids fractions of aqueous formulation used according to the present invention is in the range from 1:1 to 1:30.

It is also possible, of course, first to premix pigment and aqueous formulation used according to the present invention in a weight ratio in the range from 20:1 to 10:1 and to add further aqueous formulation used according to the present invention or a conventional acrylate binder only just before printing.

Further common auxiliaries for print pastes in textile printing are known from Ullmann, Handbuch der technischen Chemie und Verfahrenstechnik, compare for example Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, headword: Textile Auxiliaries, Volume A26, pages 286 ff and 296 ff, Verlag Chemie, Weinheim, Deerfield/Fla., Basel; 1996, and from Textil-Hilfsmittel-Katalog, Konradin Verlag Robert Kohlhammer GmbH, D-70771 Leinfelden-Echterdingen. As common auxiliaries there may be mentioned by way of example thickeners, fixatives, hand improvers, defoamers, rheology improvers, acid donors and emulsifiers.

In a further improved embodiment of the present invention inventive print pastes further comprise hand improvers selected from silicones, especially polydimethylsiloxanes, and fatty acid C₁-C₁₀-alkyl esters. Examples of commercially available hand improvers which can be added to the inventive print pastes are Acramin® Weichmacher SI (Bayer AG), Luprimol SIG®, Luprimol TX 4732 and Luprimol CW® (BASF Aktiengesellschaft).

In a preferred embodiment of the present invention inventive print pastes include as further ingredients one or more emulsifiers, especially when the print pastes contain white oil-containing thickeners and are obtained as an oil-in-water emulsion. Examples of suitable emulsifiers are aryl- or alkyl-substituted polyglycol ethers. Commercially available examples of suitable emulsifiers are Emulgator W® (Bayer), Luprintol PE New® und Luprintol MP® (BASF Aktiengesellschaft).

Inventive print pastes can be produced for example by admixing water if appropriate with a defoamer, for example a silicone-based defoamer, and adding at least one aqueous formulation used according to the present invention with mixing, for example by stirring. Thereafter, one or more emulsifiers and the pigment or pigments can be added.

Next it is possible to add one or more hand improvers, for example one or more silicone emulsions.

Subsequently it is possible to add one or more thickeners and to homogenize by further mixing, for example stirring.

A typical print paste according to the present invention comprises (per kilogram of inventive print paste in each case)

0.5 to 400 g and preferably 10 to 250 g of ethylene copolymer wax (B),

0 to 100 g and preferably 1 to 5 g of emulsifier,

1 to 500 g and preferably 3 to 100 g of thickener,

0 to 500 g, preferably 0.1 to 250 g and preferably 0.5 to 120 g of pigment (C),

if appropriate further auxiliaries;

the balance is preferably water.

In one embodiment of the present invention inventive print pastes have a 20° C. viscosity in the range from 0.3 to 4000 dPa·s, preferably in the range from 20 to 200 dPa·s and more preferably in the range from 60 to 100 dPa·s. Viscosities can be determined by common methods, especially for example with a rotary viscometer, for example the VT02 or VT24 Viscotester from Haake Mess-Technik GmbH u. Co., Karlsruhe.

Pigment printing using at least one inventive print paste can be carried out according to various processes known per se. It is customary to use a screen through which the inventive print paste is forced with a squeegee. This process belongs to the screen printing processes. Inventive pigment printing processes using at least one inventive print paste provide printed substrates combining particularly high brilliance and depth of shade for the prints with excellent hand for the printed substrates. The present invention accordingly provides flexible substrates printed by the inventive printing process using the inventive print pastes.

Another embodiment of the present invention is a pigment dyeing process utilizing at least one inventive formulation, hereinafter also referred to as inventive pigment dyeing process. The inventive dyeing process is preferably carried out by treating at least one flexible substrate, preferably a textile substrate, with at least one dyeing liquor which comprises at least one inventive formulation. Dyeing liquors comprising at least one inventive formulation are hereinafter also referred to as inventive dyeing liquors.

Inventive dyeing liquors may further comprise wetting agent additives, preferably wetting agents which are considered to be low-sudsing wetting agents, since sudsing due to the high turbulence in the dyeing operation causes the quality of the dye to be impaired from formation of unlevelnesses.

Dry textile wovens, formed-loop knits or fleece of the kind used in continuous pigment dyeing contain a large amount of air. The inventive pigment dyeing process is therefore advantageously practised using deaerators. These are based for example on polyethersiloxane copolymers. They can be included in the inventive dyeing liquors in amounts from 0.01 to 2 g/l.

Inventive dyeing liquors may further comprise antimigration agents. Useful antimigration agents include for example block copolymers of ethylene oxide and propylene oxide having molecular weights M_(n) in the range from 500 to 5000 g/mol and preferably in the range from 800 to 2000 g/mol.

The inventive dyeing liquors may further include an addition of one or more hand improvers. Hand improvers are generally polysiloxanes or waxes. Polysiloxanes have the advantage in this context of being permanent, whereas waxes are gradually washed off in use.

The viscosities of the inventive dyeing liquors are preferably in the range below 100 mPa·s. The surface tensions of the inventive dyeing liquors are to be adjusted such that wetting of the material is possible. Surface tensions of less than 50 mN/m are commercially utilized.

In one embodiment of the present invention a typical inventive dyeing liquor will comprise per liter

0.5 to 400 g and preferably 20 to 300 g of ethylene copolymer wax (B),

0 to 100 g and preferably 0.1 to 10 g of wetting agent,

0 to 100 g and preferably 0.1 to 10 g of defoamer,

0 to 300 g and preferably 1 to 20 g of antifilm agent,

0 to 100 g and preferably 1 to 50 g of antimigration agent,

0 to 100 g and preferably 1 to 50 g of leveling agent,

0.5 to 25 g and preferably 1 to 12 g of pigment (C).

A further aspect of the present invention is a process for producing inventive dyeing liquors. The process of the present invention comprises mixing colorant, for example pigment (C), preferably in the form of pigment preparations which comprise one or more surface-active compounds as well as pigment and water with above-recited additives such as further solvents, defoamers, hand improvers, emulsifiers and/or biocides and making up with water. To practise the process for producing inventive dyeing liquors, it is customary to stir the components of the inventive dyeing liquors in a mixing vessel, the size and shape of which are not critical. Stirring is preferably followed by a clarifying filtration.

A further aspect of the present invention is a process for dyeing flexible substrates using the above-described inventive dyeing liquors, hereinafter also referred to as inventive dyeing process, especially as inventive pigment dyeing process. The inventive dyeing process can be carried out in commonly employed dyeing machines. Preference is given to pad-mangles where the essential element is two squeeze rollers through which flexible substrate and especially textile is led. Inventive dyeing liquor is introduced above the rollers and wets flexible substrate or the textile. The pressure of the rollers causes the flexible substrate or the textile to be squeezed off and ensures a constant add-on level.

The actual dyeing is customarily followed by a thermal drying step and optionally a setting step. Drying is preferably done at temperatures in the range from 25 to 300° C. for a period of time in the range from 10 seconds to 60 minutes and preferably in the range from 30 seconds to 10 minutes. Setting, if setting is desired, is done at temperatures in the range from 150° C. to 190° C. for a period of time in the range from 30 seconds to 5 minutes.

Preference is given to a process for pigment dyeing by padding.

Substrates printed and dyed according to the present invention are notable for brilliance of color coupled with good hand for the respectively printed and dyed substrates. A further aspect of the present invention is therefore substrates dyed by the above-described process by using the inventive dyeing liquors.

The present invention further provides dyed flexible substrates obtainable by the inventive pigment dyeing process. Inventive dyed flexible substrates are notable for example for good wash fastnesses, good dry and wet rub fastnesses and also for good fastnesses, especially due to minimal reductions in depth of shade which are incurred in the course of the boil brush wash.

In another embodiment of the present invention flexible substrates (A) and especially foils or textile composed of polypropylene are contacted with pigment-free aqueous formulation and subsequently dried. Uncrosslinked ethylene copolymer wax uniformly distributed on flexible substrate acts as a primer and makes adhesive bonding to any other materials possible.

In another embodiment of the present invention the present invention's process for printing flexible substrates can be carried out as a transfer printing process. To this end, a paper coated with wax, for example with silicone wax, is printed with at least one inventive print paste and thereafter the printed paper is dried at from room temperature to 300° C. and preferably at from room temperature to 180° C. The dried and printed paper is treated with the textile material on a hot press or on a hot calender at 70 to 300° C., preferably for 10 to 100 s at 100 to 120° C. During this operation, the print paste softens/melts and transfers and fixes from paper onto the two- or three-dimensional flexible substrate, for example textile substrate or foil, to be printed.

Working examples illustrate the invention.

WORKING EXAMPLES

1. Preparation of Ethylene Copolymer Wax

In a high-pressure autoclave as described in the literature (M. Buback et al., Chem. Ing. Tech. 1994, 66, 510), ethylene and acrylic acid or methacrylic acid as per Table 1 were copolymerized. Ethylene was fed into the autoclave under the reaction pressure of 1700 bar at a rate of 12.0 kg/h. Separately, the Table 1 amount of acrylic acid or methacrylic acid was initially compressed to an intermediate pressure of 260 bar and subsequently fed into the autoclave under the reaction pressure of 1700 bar. Separately, initiator solution consisting of tert-butyl peroxypivalate in isododecane (amount and concentration see Table 1) was fed into the autoclave under the reaction pressure of 1700 bar. Separately, the Table 1 amount of regulator consisting of propionaldehyde in isododecane, concentration see Table 1, was initially compressed to an intermediate pressure of 260 bar and subsequently fed with the aid of a further compressor into the high-pressure autoclave. The reaction temperature was 220° C. Ethylene copolymer waxes were obtained as per Table 1 which had the analytical data evident from Table 2.

The level of ethylene and acrylic acid or methacrylic acid in the ethylene copolymer wax was determined by NMR spectroscopy and by titration (acid number) respectively. The acid number of the ethylene copolymer wax was determined titrimetrically according to German standard specification DIN 53402. The KOH consumption corresponds to the acrylic acid or methacrylic acid level in the ethylene copolymer wax. MFI was determined according to German standard specification DIN 53735 at 160° C. under a load of 325 g. TABLE 1 Preparation of ethylene copolymer waxes PO PA in in ECW T_(reactor) Ethylene AS AS MAS MAS ID ID Conversion product No. [° C.] [kg/h] [l/h] [kg/h] [l/h] [kg/h] [ml/h] c(PA) [l/h] c(PO) [wt %] [kg/h] 1.1 220 12 0.79 0.80 — — 650 25 1.95 0.07 23 3.0 1.2 220 12 — — 1.01 1.03 600 25 2.10 0.07 25 3.2 T_(reactor) refers to the maximum internal temperature of the high-pressure autoclave.

TABLE 2 Analytical data of ethylene copolymer waxes Ethylene Acid number level AS level MAS level [mg KOH/g MFI ρ No. [wt %] [wt %] [wt %] ECW] [g/min] T_(melt) [° C.] [g/cm³] 1.1 79.0 21.0 — 165 10 78-88 0.96 1.2 73.4 — 26.6 173 10 65-80 n.d. “Level” refers to the fraction of interpolymerized ethylene or acrylic acid or methacrylic acid in the respective ethylene copolymer wax. Abbreviations: AS: acrylic acid, MAS: methacrylic acid, PA: propionaldehyde, ID: isodothecane, PO: t-butyl hydroperoxide, ECW: ethylene copolymer wax.

2. Production of Aqueous Dispersions of Ethylene Copolymer Waxes

A 2-liter autoclave equipped with anchor stirrer was charged with the Table 3 amount of ethylene copolymer wax according to Example 1. The Table 3 amounts of deionized water and also ammonia were added and the temperature was raised to 120° C. with stirring. After 30 minutes at 120° the temperature was lowered to room temperature in the course of 15 minutes to obtain dispersions 2.1 and 2.2. TABLE 3 Production of aqueous dispersions of ethylene copolymer wax ECW NH₃ Water ECW amount amount amount Solids Viscosity No. No. [g] [g] [g] content [%] [s] pH 2.1 1.1 25.0 3.4 71.6 25 85 9.0 2.2 1.2 25.0 3.4 71.6 25 40 8.8 The viscosity was determined using a 5-mm cup at 23° C. to ISO 2431 “NH₃ amount” refers to the amount of 25% by weight aqueous ammonia solution.

3. Production of Inventive Print Pastes

3.1 Production of a Blue Pigment Preparation

The following were ground together in a Drais DCP SF 12 Superflow stirred ball mill:

-   2640 g of Pigment Blue 15:3 -   460 g of n-C₁₈H₃₇O(CH₂CH₂O)₂₅H -   600 g of glycerol -   2300 g of distilled water

Grinding was continued until the pigment particle had a median diameter of 100 nm.

3.2. Production of Stock Pastes

The ingredients as per Table 4 were stirred together in a stirred vessel and the stock pastes 3.1 to 3.4 were obtained by the ingredients being combined with each other, and stirred together, in the order recited in Table 4. This was followed by 15 minutes of stirring with a high-speed stirrer of the Ultra-Turrax type at about 6000 revolutions/min before the pH was tested. When the pH was below 8, a pH of 8.5 was set by adding concentrated aqueous ammonia. TABLE 4 Production of stock pastes 3.1 to 3.4 Stock paste Ingredient [g] 3.1 3.2 3.3 3.4 Distilled water — 380 — 380 2.1 980 600 — — 2.2 — — 980 600 Thickener 20 20 20 20 Sum total 1000 1000 1000 1000

2.1 and 2.2 refer to the respective aqueous dispersion 2.1 or 2.2 from Example 2.

The thickener used in each case was:

dispersion of

copolymer of acrylic acid (92% by weight), acrylamide (7.6% by weight), methylenebisacrylamide (0.4% by weight), quantitatively neutralized with ammonia (25% in water), molecular weight M_(w) about 150,000 g/mol

as water-in-mineral oil dispersion (volume ratio 2.6:1) (boiling point of mineral oil: 190-230° C.), solids content: 24% by weight; stabilized with sorbitan monooleate (2.5% by weight, based on total thickener).

3.3. Mixing of stock Pastes with Blue Pigment Preparation from Example 3.2.

Inventive print pastes as per Table 5 were produced by mixing in each case 970 g of stock paste as per Table 4 with in each case 30 g of blue pigment preparation from Example 3.1.

Inventive print pastes 4.1 to 4.4 as per Table 5 were obtained. TABLE 5 Production of inventive print pastes Stock paste No. Print paste No. 3.1 4.1 3.2 4.2 3.3 4.3 3.4 4.4

4. Printing Experiments, Tests of Prints

Substrates composed of woven polypropylene fabric, basis weight 170 g/m², were screen printed.

The printing parameters were: 15 mm squeegee, ESTAL MONO E 55 screen gauze, magnet pull level 6, simple print, no pattern.

Drying at 80° C. in a drying cabinet was followed by fixing on a fixing cabinet by heating with hot air at 110° C. for 5 minutes.

This gave the inventive substrates 5.1 and 5.2, also referred to respectively as substrates 5.1 and 5.2 printed according to the present invention.

For comparison, a print was performed with a comparative print paste V4.5 which had been produced similarly to inventive print paste 4.1 except that ethylene copolymer wax dispersion 2.1 had been replaced by a dispersion (acrylate binder dispersion) of the following copolymer:

-   n-butyl acrylate (66% by weight), -   styrene (31% by weight), -   acrylic acid (1% by weight), -   methylolacrylamide (1% by weight), acrylamide (1% by weight),     quantitatively neutralized with ammonia (25% by weight in water),     with 2% by weight, based on copolymer, of     as an emulsifier; solids content: 35% by weight.

Comparative substrate V5.5 is obtained.

The inventive substrates were tested for dry and wet rub fastness to DIN EN ISO 105-X12 and wash fastness to DIN EN ISO 105-C03. Best possible result: a rating of 5, worst possible result: a rating of 1.

The following inventive substrates and test results as per Table 6 were obtained. TABLE 6 Substrates printed according to invention and test results Rub fastness Rub fastness Wash Print paste No. Substrate No. dry wet fastness 4.1 5.1 3-4 4 3 4.2 5.2 3-4 3-4 3 4.3 5.3 3-4 4 3 4.4 5.4 3-4 3-4 3 V4.5 V5.5 3 1 1-2

6. Production of Inventive Dyeing Liquors and Pigment Dyeing

6.1. Production of Inventive Dyeing Liquors

General Recipe:

The following were mixed together by being stirred together in a stirred vessel: fully desalted water 774 g pigment preparation of  20 g/l (reckoned on pigment Example 3.1 preparation) aqueous dispersion 2.1 or 2.2 180 g/l (reckoned on solids content) EO₈PO₇EO₈  20 g/l as antimigration agent n-C₁₂H₂₅O(C₂H₄O)₇H  4 g/l as antifilm agent HO—(CH₂)₃—Si[OSi(CH₃)₃]₂  20 g/l as defoamer and made up to one liter with fully desalted water. Using aqueous dispersion 2.1 gives inventive dyeing liquor F6.1; using aqueous dispersion 2.2 gives inventive dyeing liquor F6.2.

Antimigration agent: In the EO₈PO₇EO₈ antimigration agent used in the general recipe EO is always ethylene oxide and PO propylene oxide. It has the following properties: a 40° C. cloud point in water, an average molar mass M_(w) of 1100 g/ml, solidification point<5° C., 25° C. viscosity: 175 mPa·s.

6.2. Dyeing of Substrates with Inventive Dyeing Liquors

A Mathis HVF12085 pad-mangle was used to dye a textile substrate (woven polypropylene) with in each case an inventive liquor produced according to 6.1. The nip pressure of the rolls was 2.6 bar. The resulting wet pickup was 55%. The application speed was 2 m/min. The textile was subsequently dried in an LTF89534 circulating air cabinet from Mathis at 80° C. for 60 s (air circulation 50%). The subsequent setting was carried out at 110° C. with air circulation (100%) in the course of 5 minutes.

This gave the following inventive substrates, also referred to as substrates dyed according to invention, and test results as per Table 7.

The comparative substrate was produced by dyeing with a comparative liquor which corresponded to inventive dye liquor F6.1 except that, instead of dispersion 2.1, an identical amount of acrylate binder dispersion as also used for producing the comparative print paste V4.5 was used. TABLE 7 Substrates dyed according to invention and test results Rub fastness Rub fastness Wash Dye liquor No. Substrate No. dry wet fastness F6.1 7.1 3-4 4 3 F6.2 7.2 3-4 3-4 3 Comparative V7.3 2 1 1-2 dye liquor

7. Production of Transfer Prints

7.1 Production of Inventive Transfer Printing Colors TABLE 8 Production of inventive transfer printing colors 8.1 to 8.2 Transfer printing color Ingredient [g/kg] 8.1 8.2 2.1 958 — 2.2 — 600 Fully desalted water — 358 HO—(CH₂)₃—Si[OSi(CH₃)₃]₂ 2 2 Thickener of Example 3.2 20 20 Blue pigment preparation 3.1 20 20 Sum total 1000 1000

7.2. Production of Transfer Prints

A paper coated with silicone wax was printed with the inventive print pastes, for example 8.1 and 8.2, and thereafter dried at 100° C. The printed and dried paper is treated on a hot press at 120° C. for one minute together with textile. During this operation, the print paste softens/melts and transfers and fixes from paper onto the textile to be printed. 

1. A process for treating flexible substrates, which comprises contacting (A) at least one flexible substrate selected from substrates composed of (A1) polyacrylic, polyester, silicone, polyamide or (A2) one or more polymers based on a monomer of the general formula I

in each of which R¹ is selected from —Cl, C₁-C₁₀-alkyl, —CH═CH₂, —C(Cl)═CH₂, —C(CH₃)═CH₂ and —COOC₁-C₁₀-alkyl, with at least one aqueous formulation comprising (B) at least one ethylene copolymer wax comprising from 60% to 95% by weight of ethylene and from 5% to 40% by weight of at least one ethylenically unsaturated carboxylic acid in interpolymerized form, further at least one colorant selected from (C) at least one pigment and (D) at least one dye.
 2. The process according to claim 1 wherein at least one ethylenically unsaturated carboxylic acid is a carboxylic acid of the general formula II

where R² is selected from hydrogen, branched or unbranched C₁-C₁₀-alkyl or COOH, COOCH₃, COOC₂H₅, R³ is selected from hydrogen, branched or unbranched C₁-C₁₀-alkyl.
 3. The process according to claim 1 wherein flexible substrates are selected from foils and textile substrates.
 4. The process according to claim 1 wherein flexible substrates are selected from (A2) polypropylene.
 5. The process according to claim 1 wherein flexible substrates are selected from wovens, formed-loop knits and nonwovens.
 6. The process according to claim 1 wherein at least one aqueous formulation comprises (A) at least one further material selected from thickeners, crosslinkers, film inhibitors, fastness improvers, plasticizers, defoamers, wetting agents and leveling agents.
 7. The process according to claim 1 wherein treated flexible substrate is dried after said contacting.
 8. Textile three-dimensional structures treated by a process according to claim
 1. 9. Print pastes comprising (B) at least one aqueous formulation which comprises at least one ethylene copolymer wax comprising from 60 to 95% by weight of ethylene and from 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid, in interpolymerized form, and (C) at least one pigment.
 10. Dyeing liquors comprising (B) at least one one aqueous formulation which comprises at least one ethylene copolymer wax comprising from 60 to 95% by weight of ethylene and from 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid, in interpolymerized form, and (C) at least one pigment or (D) at least one dye. 